JPS59132567A - Silver peroxide battery - Google Patents

Abstract

PURPOSE:To increase electric performance, storage life, and leakage resistance by using a positive mix mainly comprising AgO containing Cd and Te, or at least one of Pb, Hg, Tl, Ge, Y, Sn, and others in addition to Cd and Te. CONSTITUTION:A positive mix 12 mainly containing AgO containing Cd and Te, or at least one of Pb, Hg, Tl, Ge, Y, Sn, W, La, RE (rare earth elements), Zn, Se, and Al in addition to Cd and Te is pressed to form a pellet. The positive mix 12 obtained by forming an Ag2O layer 12 on its whole surface is accommodated in a positive can 11 with a separator 14 and an electrolyte absorbing material 12, and an electrolyte mainly comprising NaOH is filled. A negative can 17 with a negative material 16 is placed, then they are sealed with a gasket 18 to form an AgO battery.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver peroxide battery containing silver(II) oxide (Ar
By improving the stability in an alkaline solution and improving the positive electrode manufacturing method in (o), the electrical characteristics, storage characteristics, and leakage resistance of the battery are significantly improved.

Conventional silver oxide (D) to which no stabilizer is added is unstable because it decomposes in an alkaline solution and generates a large amount of oxygen gas.

For this reason, conventional silver (II) oxide has the disadvantage that it self-decomposes in an alkali solution, reducing its electrical capacity as silver (II') oxide. Furthermore, oxygen gas generated by the decomposition of silver (II) oxide oxidizes the separator, resulting in the separator becoming brittle, its function as a separator decreasing, and self-discharge of the battery being accelerated. '-1: Another disadvantage was that the oxygen gas generated at the positive electrode diffused and permeated through the separator to the negative electrode, oxidized the zinc, and reduced the electrical capacity of the zinc. Furthermore, when this oxidation phenomenon of zinc is promoted, the surface of the zinc is coated with a passive film such as zinc oxide, and even though unreacted zinc remains as a battery active material, battery discharge is delayed. It had the drawback of stopping.

As described above, conventional batteries using unstable silver (II) oxide as a positive electrode without the addition of a stabilizer had the disadvantage of poor storage characteristics.

1) Conventional silver (II) oxide easily decomposes in alkaline liquid and is unstable, so batteries using this silver (II) oxide gradually accumulate oxygen gas inside the battery. As a result, the internal pressure of the heavy oil becomes high, which has the disadvantage of promoting leakage of the alkaline electrolyte to the outside.

In order to eliminate this drawback, coating the surface of Ali'O particles with lead acid silver has been proposed in US Pat.
It is recorded in the book l. Since the surface of A40 particles coated with lead acid silver is difficult to reduce, the positive electrode pellet surface Vcf
The IM layer has the disadvantage of forming a VC layer, and has the disadvantage of high oil separation impedance.

271, A4dar TVarukq%J'-Fit
electrochemSac, 116.1071 (
(1969), Z n, H! , A'e
Eng n, Tt, P'b, W f 100 F3PPM?
A gas generating cap of 7 haze AyO with 1liS has been investigated.

Furthermore, in this literature, the improvement of the stability of Jl'O
To, Od, A t, P b, V, L!
Although the effect of r has been shown, it is still insufficient fz
vs.

The invention eliminates the above-mentioned disadvantages, and uses cadmium and tellurium, or cadmium and iodine, mercury, thallium, and germanium as stabilizers.

Yztrium, tin. tungsten, lanthanum, rare earths,
By using a positive electrode mixture mainly composed of silver(II oxide) containing at least one selected component such as zinc, aluminum, selenium, etc., the discharge capacity after storage can be reduced by This product is specially designed to provide a silver peroxide solution with special acidity, storage stability, and leakage resistance.

Well, let me explain about non-invention.

Using the experimental apparatus shown in Figure 1, the gas evolution t' of the silver oxide (n) powder used in the battery of the present invention and the conventional silver oxide (It) powder was measured, and the stability in an alkaline solution was compared. ! ! 2
investigated.

But, how much stabilizer do you add? I changed it and investigated the gas generating lid.

In the figure, 1 is a glass bone with a scale, 2 is a 40% potassium hydroxide aqueous solution, and 51I Go 1? Silver oxide (It) powder, 4 is constant temperature 1 carbon dioxide, and 5 is hot water at 40°C and 60°C.

〈Example 1〉 Figure 2 shows the case of mouthing an object with 65 force.
o oxygen gas) is also a diagram showing fresh blood.

6 addition ff Od O, T e 02, T A20
Gold + f for 3 form te AS'OK, 0.3% as elemental system
, 0.1%, 0.1%.

It is clear from Fig. 2 that J: ') VC, OdO + TeO
2 and CdO + TeO2 + TA203 f customer addition 7m
The oxygen gas generation i of AfO is extremely less than that of non-additive AfO.

It is clear from Table 1 that AJO is more stable in awns when various elements are added in addition to cao+'re○2.

In Table 1, caouca element is 03% relative to AgO.
, TeO2, pbo, 'rx203. ()e02. Hg
.

Te, 'pb, TR, Ge, respectively for lAgo.
0.1% of Hg (7) element is added.

In this way, the reason why silver oxide (n) containing additives becomes stable in an alkaline solution is that the ionic species of the contained metal element or metal compound is incorporated into the silver (II) oxide crystal lattice. It is presumed that this is because the crystal structure is strengthened by the stabilization, but the exact stabilization mechanism is unknown.

<Example 2> FIG. 5 is a diagram showing the relationship between the amount of fl Ca and Te added to Ago and the amount of oxygen gas generated.

In addition, the numbers in the figure are A g O1t +7) 40℃
, shows the amount of gas generated after 240 hours in a 40% K o H aqueous solution.

Cd and Te are 0dO):, A as a compound of TeO2
It was not added to go.

From the figure, as the amount of CD added increases, the amount of oxygen gas generated decreases. On the other hand, the amount of Te added is 0.05 to 0.
．． It can be seen that the amount of oxygen gas generated decreases within the range of 3%.

If you add a lot of these additives, AgO? : Since the capacity of the main positive electrode mixture decreases, in order to secure electricity and at the same time minimize the amount of oxygen gas generated,
:Tθ=0.3%:0.1% (CdO:Te02=0.
34%2013%) were selected.

Hereinafter, the present invention will be described in detail using Ago to which additives have been added with a composition of Cd:Te:Tn=0.320, 1:0.1%.

<Example 6> Table 2 Chemical 'and physical pr
opertiesAgo Ago Co 02 ga
s AE+, 2 CO3Aver Hibiki Ap[BT'ent
Ap[B1”ant-tent=singCont
ent Brticle density tappi
ng (%) Volume (%) 5ize
(ji'/cC) density (μψ0Uhr)
'(μ)(1/ω)廿-〇KOH 40℃ New 9B, 3 16 0.41
2.96 0.79 1.95 Table 2 shows CdO, TeO2, and Tn203 in Ag.

For Cd: Te: T4J= 0.3: U
, 1 : added at a ratio of 0.1% f(A) to show the chemical and physical properties of gO.

The vf technique has a high AgO content M' and a small amount of oxygen gas generated. Furthermore, since the average particle size is large, and the bulk density and tap density are also large, Ag.

It also has the advantage of good powder flowability and improved pellet formability.

<Example 4> Figure 4 shows Od:Te:TR=0.3:[11,1:0.1 for CdO, TeO2, TfizO3kAg○.
It is a figure showing the relationship between Ag◯ content and time for Ago added at a ratio of % and conventional Ago to which no additives were added.

Quantitative analysis of Ago-containing water was carried out using a conventional method generally employed, that is, a potassium iodide reduction titration method.

The AgO sample was immersed in 40% KOH at 60°C.
Ago content was quantified every 20 days.

From this figure, after 40 days of immersion storage, the vertical difference in Ago content becomes larger, and the conventional AgO content decreases to 30% on the 60th day and 10% on the 80th day.

On the other hand, the Ago according to the present invention had 50 Ag on the 200th day.
It can be seen that the O content is maintained and is significantly stabilized over a long period of time.

<Example 5>.

Ag according to the present invention explained in Examples 3 and 4.

Assemble the battery according to the invention using the holes.

FIG. 5 is a sectional view of a battery showing one example of the present invention.

In the figure, reference numeral 11 denotes a positive electrode can, which houses a positive electrode mixture 12 covered with a reduced silver layer 13, a separator 14, and an electrolyte impregnating agent 15. The electrolyte is an alkaline solution mainly containing sodium hydroxide.

The positive electrode mixture 12 is made of a mixture of 95 to 9-94 parts by weight of silver (II) oxide powder used in the battery of the present invention and 1 to 5 parts by weight of tetrafluoroethylene powder, and is molded under pressure.

- In addition to polytetrafluoroethylene powder, as an organic binder, we can also use lubricity, which is a necessary property for pressure molding.
Is it a substance that has binding properties and is oxidation and alkali resistant?
：If it is a stable substance, it is suitable for use as an official.

For example, olefin resin powders such as polyethylene and polystyrene, polyamide resin powders such as nylon, water-bathable polymer powders such as carboxymethyl cellulose, polyvinyl alcohol, and sodium polyacrylate are suitable as organic binders.

In addition to the organic binder described above, any liquid such as a dispersion solution or a water bath liquid can be used.

Note that the lower limit of the binder-added piece is 1% due to the binding effect. Although there is no particular upper limit, if it exceeds 5%, the amount of silver oxide (■) in the positive electrode mixture decreases, resulting in a decrease in battery capacity. Furthermore, if you add more than 5 parts,
Since these binders are electrically insulating substances, the electrical resistance within the positive electrode mixture increases and the internal resistance of the battery increases.

Therefore, in the present invention, the amount of binder added is 1 to 5%.
is appropriate.

Note that even if the amount of the binder added exceeds 5%, the stability of the silver (II) oxide used in the battery of the present invention is not impaired.

Further, in the figure, 15 is a silver layer provided on the surface of the positive electrode 6 agent 120. This silver layer 13 is formed by reducing the entire surface of the positive electrode mixture 12 using an appropriate reducing means.

17 is a negative electrode can, which contains a negative electrode mixture 16Jr consisting of a mixture of frozen zinc powder and one or two gelling agents such as carboquine methylcellulose and sodium polyacrylate:
It is stored. This negative tide mixture 16il-i' can be used either by stirring or in the form of a gel together with an alkaline electrolyte.

Moreover, there is no problem even if this negative electrode mixture 16 is lightly pressurized.

18 is a sealing gasket that electrically insulates the negative electrode and the positive electrode. This 18 is made of polyamide resin.

First, Tu726sw (outer diameter Z8 thickness, height 2.6 sections, Z
The self-discharge rate of the (n/NaOH/Ago) battery was investigated, and the results are shown in FIG.

Storage test method 1 is to discharge the battery into a constant lake tank at 60°C, and after 20 or 40 days, remove the battery from the tank and discharge it to a load resistance of 7.5 Ω to determine the remaining capacity. .

Self-discharge rate was calculated after storage at 60°C for 20 or 40 days. The self-discharge rate was calculated from the following formula.

Data are average values of n=24.

Furthermore, the self-discharge rate of the battery, which was stored at room temperature for 14 months after battery manufacture, was also compared with that of a conventional battery.

The self-discharge rate after storage at 60°C for 40 days was reduced to 1/3-2 compared to conventional ponds.

Furthermore, the self-discharge rate after storage for 14 months at room temperature is reduced to '/L35 to l//2.8 compared to conventional batteries.

Next, we investigated the low-temperature characteristics of the battery. The results are shown in Figure 7 (a
), (b), and (C).

The closed circuit voltage at −10°C is Z8 at RL = 2 KΩ
This is the voltage during υtsec pulse discharge.

The battery of the present invention has n=10 x5, and the conventional battery has 10 lots of x
shows.

From FIG. 7, it can be seen that although the low-temperature closed circuit voltage of the battery of the present invention is low in the initial stage, its change over time is small.

The Ag according to the present invention has a smaller change over time in the low temperature closed circuit voltage of the battery of the present invention than that of conventional batteries.

This is because the silver layer formed on the surface of the positive electrode is less likely to be oxidized by the decomposed oxygen gas of Ago, and the zinc used in the negative electrode is less likely to be oxidized, since it is stable in an alkaline aqueous solution.

As in Examples 1 to 5 described above, the present invention has excellent storage characteristics and little change over time in low-temperature circuit voltage.
A highly reliable silver peroxide battery can be provided.

However, heavy oil for high current (Zn/KOH/At;<
When AEI, O according to the present invention is used for 0), the low-temperature closed circuit voltage immediately after battery manufacture is 7
0-10077 When the LV is low, there are still issues to be solved.

The challenges are: 1) Optimization of the amount of additives such as Ofio, TeO2, TR203, etc. 2) Adjustment of the silver layer formed on the surface of the positive electrode using this Ago and Ag
00 and 3) In the same reduction-1, the thickness of the reduced silver layer on the positive surface using this Ago is equal to that of the conventional positive electrode using AgO. I was able to resolve the issue by doing the following.

Examples of these solutions will be shown below in Examples.

<Example 6> First, a sister example will be shown in which the amounts of additives such as CdO, TeO2, and TR203 were optimized.

FIG. 8 is a diagram showing the relationship between the amount of stabilizer added and the amount of oxygen gas generated.

In the figure, A is OdQ+TeO2 as a stabilizer, and B is cao-1-Teoz+Tfizo3 as a stabilizer.

The point where -ti, addition amount - is zero is the amount of oxygen gas generated by the conventional silver (II) oxide powder.

As is clear from FIG. 8, it can be seen that oxygen gas is generated less in case B than in case A.

This is because thallium oxide was added in addition to cadmium oxide and tellurium dioxide.

Furthermore, from FIG. 8, it can be seen that as the amount added increases, the amount of oxygen gas generated also decreases.

Addition-1J 5000 to 10000 PPMT produces the least amount of oxygen gas.

The form of the shredded, stiff-containing component has a great effect on the stability of silver(II) oxide in an alkaline solution, even in the case of metal elements or metal compounds.

Next, it was assembled in the same manner as in Example 5 of the present invention using silver oxide (It) powder with different addition tv of the stabilizer.

However, the battery of this example is TR926W (outer diameter 9.5
wtt, height 2.6 wn, Zn/Ko
H/A gO, nominally 52 mA h).

After manufacturing this battery, the battery was stored at room temperature for 6 months and its low temperature characteristics, self-discharge rate, and leakage rate were investigated. Table 6,
Table 4 shows the results.

Low-temperature characteristics are determined by placing the battery in a -10°C thermostat.
In the measurement circuit shown in the figure, switch S is closed, and then the lowest closed circuit voltage (if 'i) is read with a voltmeter (■) within 5 seconds.The data shows the average value of n=10.

Table 6 Table 4 Storage characteristics test method (measuring self-discharge rate): Leave the battery in a thermostatic chamber at 60°C, and after 40 days, remove it from the chamber and discharge it with a load resistance of 7.5 KΩ. Find remaining capacity.

It was given by the following formula (2).

However, each initial cycle is the battery capacity before storage.

Data are average values of n-24.

The leak test method is to test the battery at 60℃ and relative humidity of 90-95%.
After 1000 hours, the battery was taken out from the tank and observed for leakage (f- observed with a stereomicroscope.Leakage was observed on the outer surface of the battery negative electrode can; iL*: marked something as defective.

The data shows the leakage rate for n=100.

Table 3 shows the results of investigating the low-temperature characteristics, self-discharge rate, and leakage rate of the battery by varying the amount of stabilizer made of cadmium oxide and tellurium dioxide. Composition of stabilizer was set to approximately CaO:Te02=6-1.

In the table, conventional batteries contain silver oxide (silver oxide) that does not contain a stabilizer.
Batteries A to G of the present invention are batteries using silver (II) oxide in which the amount of stabilizer added is varied from 10 to 110,000 PP.

As is clear from Table 5, the batteries A to G of the present invention have a lower self-discharge rate and a lower leakage rate than the conventional batteries.
It can be seen that this is an extremely superior 11fC battery.

Self-discharge rate and leakage W7 of a battery using silver oxide (n)e without the addition of this stabilizer. The reason for the low incidence is that silver (II) oxide that does not contain a stabilizer gradually decomposes when it comes into contact with an alkaline electrolyte.

If this silver oxide (l) decomposes, 1) Decrease in the capacitance of silver oxide (ll) 2) Oxidation 8 (■
) and deterioration of the separator due to decomposition of oxygen gas and i[fL
Lead consumption 3) Decomposition of silver oxide (It) Accumulation of oxygen gas causes an increase in battery internal pressure.

On the other hand, the reason why the battery of the present invention is superior is that silver oxide (n)
This depends on the effect of the stabilizer contained in the.

The stabilizers are in the form of oxides and hydroxides.

Whether it is metal powder, sulfide, or various substances, it has a great effect on the stability of silver (II) oxide in an alkaline solution.

It can be seen that the low temperature property 1:j is closely related to the amount of stabilizer added.

That is, as the amount of stabilizer added increases, the low-temperature properties worsen.

The reason for this is that the stabilizer stabilizes the silver oxide (n)k and discharges a large current of RL = 2 ohm.
In the first case, it is presumed that the discharge reaction of silver oxide (11) becomes rate-determining, and the low-temperature characteristics deteriorate.

In the case of a liquid watch with a lamp and a 1 yen 3 display type digital watch, 105 mm is required as the low humidity characteristic, so taking into account variations etc., the low temperature characteristic value of the 4 yen pond F of the present invention is considered to be the lowest limit value. That doesn't seem reasonable.

That is, the addition of stabilizer♀ is 10 to 5000 PPM
Within this range, it is possible to increase the self-discharge rate and leakage rate higher than conventional batteries while maintaining the low-temperature characteristics at appropriate values.

Next, Table 4 will be explained.

Table 4 shows the results of investigating the low temperature characteristics, self-discharge rate, and leakage rate of the battery by varying the amount of stabilizers made of cadmium oxide, tellurium dioxide, and thallium oxide; similar to Table 3. It is.

The composition of the stabilizer was set to be approximately C: O: TeO: T: 1:1, as shown in Table 5.

As shown in FIG. 8, the stabilizer is CdO.

Teo2. Silver oxide (It
)(7) generates less oxygen gas in alkali IJi than silver oxide (11) consisting of two components of C, 10, and TeO2, and is more stable.
Compared to the battery A-() of the present invention, the self-release rate and the rate of leakage are further reduced, and it can be seen that the battery is superior.

On the other hand, as in Table 3, the low-temperature characteristics 1 of the batteries A' to G' of the present invention continue to decrease as the amount of stabilizer added increases.

Furthermore, the batteries E' to G' of the present invention are the batteries E' to G' of the present invention.
The low-temperature properties are even worse than that of . The reason for this is that the silver oxide (n) used in the batteries E' to G' of the present invention is
Since it is more stable than silver(II) oxide used in the battery E-() of the present invention, as a reaction, RI = 200
It is presumed that this is because the IR polarization is large compared to the discharge reaction at Ω.

As detailed above, the present invention (1,10 to 5000 PPM
To provide a silver peroxide battery having excellent storage characteristics and leakage resistance while maintaining good low-temperature characteristics by using a positive electrode mixture mainly composed of silver oxide (If) containing all the stabilizers of be able to.

Furthermore, silver (II) oxide can be produced using conventional silver (It) oxide.
The battery produces a battery voltage of 1.55 V, and the oxidized steel (II) used as the positive electrode is treated with a hydrogenation process to form a silver layer on the surface of the oxidized silver (II). 1.8
5 V (potential difference between silver(II) oxide and zinc) was erased.

However, as the silver layer changes over time, it gradually oxidizes and changes to silver oxide (1), resulting in a high potential (ta5v).
) had the disadvantage of appearing.

This is because when forming a silver layer on the silver oxide (n) surface, when a silver oxide (+) layer is formed between the oxidation director (1) and the silver layer, some of the silver oxide (1) layer is This is because metallic silver is generated.

Therefore, there is no electronic insulation between silver(II) oxide and the silver layer, and the silver layer on the surface undergoes re-oxidation, resulting in the following reaction:
The present invention completely eliminates the above-mentioned drawbacks, and examples thereof will be described below.

Examples Cadmium oxide (CdO) powder 01 parts by weight, tellurium oxide (TeO2) powder 006 parts by weight (i-silver oxide (Il) (
AgO) powder was added to 95 parts by weight, and further 5 parts by weight of tetrafluoroethylene powder was added and mixed for 1 hour. The agglomerate was sized and then pressure-molded at 8 ton/cr, 4 to produce pellets. Next, 9 including 10 chi KoH
After being immersed in a 00 parts by weight methanol solution for 30 minutes, it was washed with water.

The sample was immersed in a 20 wt% KoH aqueous solution with a liquid temperature of z 60'C for 15 minutes.Next, it was immersed in a 500 parts by weight ethanol solution containing 0.5% hydrazine for 3 minutes, taken out from the solution, and dried at room temperature. and stored in a desiccator.

I made berets with different amounts of additives in the same way as described above.

Example 101 parts by weight of cadmium oxide (CdO) powder, tellurium oxide (TeO2) powder (3,003%!Itfls) and 0.0 parts by weight of thallium oxide (I[[) (T ih 03) powder].
[ ] 03 parts by weight were added to 95 parts by weight of silver oxide (It) (AgO) powder, and further 5 parts by weight of tetrafluoroethylene powder were added and mixed for 1 hour. After sizing the mixed powder, 8
Pressure molded at tOn/cA and placed it in a positive electrode can.
child.

Next, it was immersed for 1 hour in a 500 parts by weight methanol solution containing 0.1% by weight of tartaric acid and 5 times double densities of KoH, and then washed with water. 10% KoH with an additional 2% by weight of potassium persulfate
After being immersed in the aqueous solution for 15 minutes, it was thoroughly washed with water. Next, in a 100 parts by weight KOH aqueous solution containing 1-fold tartaric acid, 2
It was immersed for 0 minutes. After this reduction, it was dried at 40 to 50°C and stored in a desiccator. In the same manner as described above, pellets with different amounts of additives were also produced.

<Example 9> Cadmium hydroxide (ca(oH)z) powder 0.1 part by weight, tellurium hydroxide [Te(OH)6] powder 0.03 parts by weight, and thallium hydroxide [TλOH] powder α0 powder α0 gold 4 parts by weight of Ren powder was added and mixed for 1 hour. After the mixed powder was completely sized, it was press-molded at 8 ton/r:rA, and left in a positive electrode can. This 'rL was immersed in a methanol solution containing 1% KOH for 30 minutes and then washed with water. Furthermore, it was immersed in a 20% KOH water bath solution at a temperature of 60° C. for 15 minutes, and then washed with water. Next, 50% containing 0.5% hydrazine
After being immersed in a 0 parts by weight ethanol solution for 6 minutes, it was taken out from the solution, dried at room temperature, and stored in a desiccator. Berets with different amounts of additives were also produced in the above manner.

Using the positive electrode mixture prepared as described above,
A silver (II) oxide battery as shown in FIG. 5 was assembled.

TR926W was assembled into a battery in the same manner as in Example 6.

After manufacturing the battery, store it at room temperature for 3 months'f? The low-temperature characteristics, self-discharge rate, and leakage rate of the L battery were investigated.

Table 5 shows the results.

Table 5 As is clear from Table 5, the self-discharge rate and leakage rate of the batteries of the present invention are lower than those of the conventional batteries.
It turns out that it is an extremely excellent battery.

From Figure 8 and Table 5, the amount of additives that reduces self-emission 1k while keeping the low-temperature characteristics at an appropriate value is 10 to 5000PP.
It can be seen that the range is M.

FIG. 10 shows the change in internal resistance of the conventional battery and the battery of the present invention after storage at 60°C. As is clear from this figure, the internal resistance of the conventional battery increased after 40 days of storage, but the internal resistance of the battery of the present invention hardly increased even after 80 days of storage.

The reason for this is that the @ layer 16 and the silver (II) oxide 12 are completely insulated. That is, by reoxidizing the silver to silver oxide (1) through oxidation treatment, the silver oxide (+) and -Togin produced after the KOH-methanol reduction performed in Examples 7 to 9 of the present invention are , since it isolates the electronic leads of silver and silver oxide (11),
This is because reoxidation of the silver layer 12 does not occur.

As detailed above, the battery of the present invention contains additives of 10 to 50%.
The silver oxide (It) containing 0'OPPM is subjected to a weak reduction treatment and then an oxidation treatment to completely insulate it from the silver layer that will be formed later, thereby maintaining good low-temperature characteristics.
It is possible to provide a silver oxide (■)' battery that completely prevents increase in internal resistance and has excellent storage stability and leakage resistance.

Finally, when the positive electrode surfaces using the Ago of the present invention and the conventional Ago are subjected to reduction treatment with the same amount of reduction, 7, the thickness of the reduced silver layer on the surface of the positive electrode according to the present invention, 21.
The following examples will show that the low-temperature closed circuit voltage of the battery can be improved by using f as the positive electrode using conventional Ag0f.

Example Using the present invention Ag○ and the conventional Ago meeting, TR616SW (
A positive electrode pellet with an outer casing of 6.81 B and a casing of 1 and 6: elutriation was prepared, and a silver layer was formed on the surface of this pellet by reduction treatment.

In the Ago of the present invention, CdO, Te0z, and Tj1203 are added as Oa, Te, and TR in amounts of 0.6%, 0.1%, and 0.1%, respectively.

Table 6 shows the silver layer thickness (A), reduction processing amount (B), and p-/ of the positive electrode pellet for the Ago of the present invention and the conventional Ago.
Indicates B.

Table 6 As is clear from Table 6, this Ago is different from the conventional Ago
Because it is very stable compared to conventional Ago, the silver layer on the surface of the positive electrode during the reduction treatment is thinner than conventional Ago, and the closed circuit voltage of the battery at low temperature is thought to be 70 to 100 roV lower than that of conventional batteries.

Therefore, 4.4 μ/m A on the surface of the positive electrode according to the present invention.
It can be seen that if a silver layer of up to about 81μ/ynAh is formed at a temperature of more than h, the low-temperature closed circuit voltage will improve and the heat will be improved.

In addition, if this example and the sister examples 6 to 9 described above are used together,
The improvement effect becomes even more noticeable.

As detailed above, the battery of the present invention can provide a silver peroxide battery that has excellent storage characteristics and leakage resistance while maintaining good low-temperature characteristics, and its industrial value is extremely large. It is ideal for pacemakers, electronic watches, cameras, trains, hearing aids, etc.

[Brief explanation of drawings]

Figure 1 is a cross-sectional view of the gas measuring device, Figure 2 is a diagram showing the amount of 02 gas produced by Ago with various additives added, and
The figure shows the relationship between the CD addition effect, the Te addition amount, and the 02 gas generation/meter.
Figure 5 is a cross-sectional view of a battery showing an embodiment of the present invention; Figure 6 is a diagram showing the relationship between the number of days immersed in 40% KOH at 60°C and the Ag○ content. Graphs showing the relationship between period and capacity reduction rate, Figure 7 (a,), (b)
, (c) is a graph showing the relationship between room temperature storage period and voltage stability, Figure 8 is a graph showing the relationship between additive addition 11- and 02 gas generation content, and Figure 9 is a measurement circuit for low temperature characteristics. 10 are graphs showing the relationship between storage period and internal resistance. 1...Glass tube part with scale 2...40% potassium hydroxide water bath solution J...Silver (II) oxide powder 4...Thermostatic bath 5.
...Mixed water at 40℃ 11...Positive electrode can 12...lE
Pole mixture 13... Reduction i layer 14... Separator 15... Electrolyte impregnated material 16... Negative electrode mixture
17... Negative electrode can 18... Sealing gasket
B...Battery to be measured R...200Ω load resistance 811. Yuichi ■・・・Voltmeter weight Upper applicant: Daini Seidokusha Co., Ltd. Agent Patent attorney Tsutomu Mogami

Claims (1)

[Claims] (1) Cadmium and tellurium, or these two components include lead mercury, thallium, germanium, yttrium,
Tin, tungsten, lanthanum, rare earths. A silver peroxide battery characterized in that the positive electrode is a positive electrode mixture mainly composed of silver oxide (n) containing at least one component selected from zinc, selenium, and aluminum. (2) A metal-free silver oxide (1) layer is provided on the entire surface of the molded body of the positive electrode mixture, and further a silver layer is provided on a part or the entire surface of the silver oxide layer (1). A silver peroxide battery according to claim 1. (3) A silver layer is provided on a part or the entire surface of a positive electrode pellet or positive electrode unit made of a positive electrode mixture mainly composed of silver oxide (11) containing said component. Silver peroxide battery according to item 1. (4) Claim 1, wherein the positive electrode mixture consists of silver (II) oxide and an organic binder. The silver peroxide battery according to item 2 or 3. (5) The total added amount of the ingredients is 10% relative to silver oxide (n).
The silver peroxide battery according to claim 1, 2, 5, or 4, characterized in that the silver peroxide battery contains 500 [IPPM]. (6) Relationship between the thickness (A) of the silver layer formed on a part or the entire surface of the positive electrode pellet or positive electrode unit and the amount of reduction treatment of silver (II) oxide in the positive electrode mixture (B) A/B =
4.4 to a1μ/mA h
The silver peroxide battery described in Section 1. (7) Claims 1 and 2, characterized in that an alkaline electrolyte mainly containing potassium hydroxide is used;
The silver peroxide battery according to item 3, 4, 5, or 6. (3) The silver peroxide according to claim 7, wherein the open circuit voltage is 1.62 V or less, and the 2000 constant resistance discharge voltage at -10°C can be maintained at 1.5 V or more for 5 seconds or more. battery.